DK156662B - APPLICATION OF ALCOHOL-SOLUBLE POLYAMIDS AS PRINT COLOR BINDING AGENT - Google Patents

Abstract

Polyamides which are alcohol-soluble at room temperature, are useful in formulating printing inks, and which comprise dimerized fatty acids, at least one aliphatic unbranched monocarboxylic acid and at least one aliphatic branched monocarboxylic acid as the acid component, and ethylenediamine and hexamethylenediamine as the amine component, and printing inks formulated therefrom.

Description

DK 156662 B

The invention relates to the use of alcohol-soluble polyamides at room temperature prepared by the condensation of A) dimerized fatty acids with 5 B) tnonocarboxylic acids and C) ethylenediamine and 10 D) unbranched co-diamine, and in given E) inorganic and / or organic pigments. and / or soluble dyes, waxes, germicides, antioxidants, nitrocellulose, and / or blended resins, 15 so inks for printing inks.

In the production of inks, the ink industry is increasingly demanding, in addition to the required good solubility at room temperature in alcohols such as propanol, butanol and especially ethanol, as well as a good all-carbon dilution in goodness, as well as a good water resistance of the grounded printing film.

The good readability at room temperature is required to ensure that, after a standstill of the printing roller, the film re-read is immediately re-read by the printing process. If the dried film does not or does not immediately dissolve, prints will be full of errors and thus useless.

30 The good dilution - especially ethanol dilution - is downward, so that the resin does not precipitate at large instantaneous concentration changes, but remains in solution. Large point changes in concentration occur when, by evaporation loss, it is necessary to re-adjust thickened 35 inks to the lower viscosity by the addition of pure solvent. The resulting lower resin concentrations may lead to a precipitation of the resin or to cloudiness in the solution, which in this state no longer

DK 156662 B

2 gives glossy prints, ie. errors and thus useless pressure also occur.

A good water resistance of the inks is required rather than ait, where the printed items are exposed to elevated moisture concentrations, such as e.g. by freezing storage of packaged foods, carrier bags, etc.

The use of alcoholic polyamides on the basis of dimerized 10 fatty acids for the production of inks is known already, although these products still show deficiencies.

According to DE Patent No. 1,520,940, polyamides are used on the basis of dimerized fatty acids, an unbranched aliphatic mono-carboxylic acid having 1-5 carbon atoms, ethylenediamine and an unbranched c-o-diamine having 4-10 carbon atoms as a printing ink binder. While Diss® polyamides are dissolved equally in ethanol and exhibit good water resistance, they do not have adequate ethanol dilution and no satisfactory gelling resistance of the solutions especially at temperatures below room temperature.

According to DE Patent No. 1,645,408, plyamides are used on the basis of dimerized fatty acids, an unbranched aliphatic monocarboxylic acid having 1-5 carbon atoms, ethylenediamine and aromatic or cycloaliphatic co-diamines as printing ink binder. While these products are soluble in ethanol and exhibit good ethanol dilution, they have poor water resistance and no satisfactory gelling resistance of the solution.

U.S. Patent No. 3,412,115 discloses polyamides based on dimeric fatty acids, an alkylene diamine having 2 to 3 carbon atoms and hexane monocarboxylic acids, and optionally additional monocarboxylic acids, as well as their use as a printing ink binder. However, these products exhibit an unsatisfactory adhesion to the printed article and show poor ethanol thinness and no sufficient gelling resistance of the solution, especially at temperatures below room temperature.

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DK 156662 B

From US Patent No. 3,700,618, polyamides are known for use in alcoholic solution as binders for printing in which polyamides form mixtures of monocarboxylic acids.

The inks obtained have improved freeze-thaw properties. However, an essential prerequisite for achieving these properties is a special selection of the polymeric acids and that they are used in critical proportions. The patent does not provide instructions on how to obtain a good alcohol tolerance.

10 °

The object of the invention is to overcome these disadvantages and to find polyamides for use as printing ink binders which, in addition to a good alcohol solubility at room temperature, also exhibit a good alcohol dilution, a good gelling resistance of the solution at temperatures below room temperature, such as hot block point as possible of ΐςνΚίί ^ βη, as well as good heat resistance.

This is achieved according to the invention by using the species mentioned in the introduction, characterized in that component A is made of dimerized fatty acids of 16-24 carbon atoms, component B comprises B 1) at least one aliphatic, unbranched monocarboxylic acid of 3 -6 carbon atoms and 2) at least one aliphatic branched monocarboxylic acid of 4-9 carbon atoms, the equivalent ratio of components A and B ranging from 0.73: 0.27 to 0.6: 0.4 and each of the compositions. -35 nents B 1) and B 2) are present in quantities of at least 0.1 equivalents calculated on the total amount of acid equivalents, that component D is hexamethylenediamine and that 4

DK 156662 B

the equivalent ratio of components C to D ranges from 0.7: 0.3 to 0.4: 0.6.

The present invention while used dimerized fatty acids 5 according to component A) are the commercially available technical polymerized fatty acids. The term dimerized fatty acids generally refers to polymerized acids which are obtained by "fatty acids". The term "fatty acids" includes unsaturated, natural and synthetic one-base aliphatic acids 10 having 12-22 carbon atoms, preferably 18 carbon atoms.

These fatty acids can be polymerized by known methods (cf. DE-OS 14 43 938, DE-OS 14 43 968, DE-PS 21 18 702 and DE-PS 12 80 852).

Typical commercially available polymeric fatty acids have approximately the following composition: monomeric acids (Mo) 5-15% by weight dimeric acids (Di) 60 - 80% by weight 2o trimeric acids (Tri) 10 - 35% by weight

The dimeric acid content can be increased to 100% by weight by commonly known distillation methods.

The monocarboxylic acid mixture used in accordance with the invention according to B) consists of 1) at least one aliphatic, unbranched monocarboxylic acid having a chain length of 3-6 carbon atoms such as propionic acid, n-valeric acid, n-capric acid and especially butyric acid One aliphatic branched monocarboxylic acid having 4-9 carbon atoms such as iso-butyric acid, iso-capric acid, iso-heptanoic acid, iso-octanoic acid, iso-nonanoic acid and especially 3-methylbutyric acid and 2-ethylhexanoic acid.

According to the invention, the combination of one of the acids mentioned under B 1) and one of the acids mentioned under B 2) is preferred.

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DK 156662 B

The ratio of the polyxnerized fatty acid according to A) to the combination of the monomeric fatty acids according to B) is between 0.73: 0.27 to 0.6: 0.4 equivalents, especially 5: 0.7: 0.3, calculated on the total amount of acid equivalent.

The amount of the monocarboxylic acid combination according to B1) and B2) from 0.27 - 0.4 equivalents, calculated on the total amount of acid equivalent, can be divided into alternating amounts between components B1) and B2), however each of the components B1) and B2) must be present in quantities of at least 0,1 equivalents, calculated on the total amount of acid equivalent.

In order to modify the properties of the final products, in addition to components A - D of the invention, smaller amounts of other reactive components, such as long-chain diamines in particular, can be used, the quantities having to be selected at all times so that neither the alcohol solubility, the dilution, the gelling and the water resistance are selected. , as well as the block point of the polyamides, must be lowered below the value needed in practice.

The acid components A) and B) and the amine components C) and D) are substantially in equivalent amounts. For the modification of the properties, less than 25 deviations are possible for one side or the other.

As a solvent for the preparation of the inks, all the usual short-chain, aliphatic alcohols of 2-4 carbon atoms, such as 3Q such as n-propanol, iso-propanol, butanol, iso-butanol and especially ethanol, are added as well as the modification. of the usual esters and ketones in this area ^ in consideration.

The ink solutions are set to a usual content of approx. 20 - 50 percent fat, preferably 25 - 35 percent, corresponding to an expiration time of 18 - 25 seconds measured in DIN 4 mm beaker according to DIN 53 211.

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In addition to the inks, the usual inorganic and / or organic pigments or soluble dyes, waxes, lubricants, antioxidants, nitrocellulose, blended resins, etc. may also be used in this field.

The inks used in accordance with the invention are used in the printing sector especially for deep or flexo printing.

10

Example 1 600 g of dimeric fatty acid (D 75) is applied with 44.55 g of propionic acid and 30.7 g of iso-valeric acid (equivalent ratio of 0.7: 0.2: 0.1) in a stirrer, thermometer and cools the three-necked flask. The flask is evacuated three times and nitrogen is added. To it are added 52.06 g of ethylenediamine (EDA) and 125.9 g of hexamethylene diamine (HDA as 60 percent in aqueous solution) and the components are heated in a nitrogen-2q atmosphere while stirring for two hours to 240 ° C.

The temperature of 240 ° C is kept for 4 hours. After two hours, a vacuum of approx. 20 mm.

Hg. The product shows ^ acid number of approx. 2 and an amine number of approx.

1.5 and has a softening point of R + B 114 ° C. The examples listed in Table 2g 1 were prepared analogously as described in Example 1.

30 35 7

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Table 1 5

Eczime dimer fat chain switch

. I II

column acid 1,600.00 g D 75 44.55 g propionic acid 30.70 g iso-valeric acid 10 2 600.00 g D 75 44.55 g 43.30 g ethylhexanoic acid 3 308.00 g D 75 17.20 g "33.30 g 4 300.00 g D 75 22.28 g" 24.26 g isononic acid 5 600.00 g D 75 53.02 g butyric acid 26.51 g iso-butyric acid 6 600.00 g D 75 53, 02 g "30.70 g iso-valeric acid 7 7 825.00 g D 75 72.90 g" 59.55 g ethyl hexanoic acid 8 320.00 g D 75 28.27 g "27.46 g isononanoic acid 9 320.00 g D 75 14.14 g "45.94 g ethyl hexanoic acid 10 320.00 g D 75 28.27 g" 16.62 g iso-valeric acid 11 340.00 g D 75 35.28 g n-valeric acid 15.02 g iso butyric acid 20 12 300.00 g D 75 28.55 g butyric 25.16 g iso-valeric acid 13 340.00 g D 75 26.29 g 28.36 g isononanoic acid 14 300.00 g D 75 50.98 g capric acid 37.88 g ethyl hexanoic acid 360.00 g D 75 31.80 g butyric acid for 9.21 g iso-valeric acid (13.00 g ethyl hexanoic acid 25 16 360.00 g D 75 31.80 g "18.42 g iso -valeric acid 35 35

- DK 156662 B

8

Table 1 (continued) 5

Eczema equivalent EDA 60% ig equivalent R + B

island

pel ratio HDA ratio C

1 0.7: 0.2: 0.1 52.06 g 125.90 g 0.575: 0.425 114 2 0.7: 0.2: 0.1 45.27 g 148.10 g 0.5: 0, 5 87 10 3 0.7: 0.15: 0.15 26.72 g 64.62 g 0.575: 0.425 91 4 0.7: 0.2: 0.1 22.64 g 74.06 g 0.5 : 0.5 94 5 0.7: 0.2: 0.1 52.06 g 125.90 g 0.575: 0.425 113 6 0.7: 0.2: 0.1 52.06 g 125.90 g 0.575 : 0.425 114 7 0.7: 0.2: 0.1 74.75g 177.50g 0.575: 0.425 100 15 8 0.7: 0.2: 0.1 24.87 g 81.08 g 0.5: 0.5 96 9 0.7: 0.1: 0.2 27.36 g 72.98 g 0.55: 0.45 72 10 0.7: 0.2: 0.1 19.90 g 97, 30 g 0.4: 0.6 102 11 0.7: 0.2: 0.1 30.39 g 73.22 g 0.575: 0.425 109 12 0.65: 0.20: 0.15 28.87 g 69.58 g 0.575: 0.425 111 20 13 0.72: 0.18: 0.10 29.54 g 71.19 g 0.575: 0.425 98 14 0.60: 0.25: 0.15 26.41 g 86 , 11 g 0.5: h, 5 95 15 0.70: 0.20 27.70 g 90.77 g 0.5: 0.5 98 0.05: 0.05 16 0.70: 0.20 : 0.10 27.70 g 72.62 g 0.5: 0.4: 0.1 100 2 18.51 g 1,12-diamino-dodecane 35

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9

Table 1 (continued) 5

Comparative Examples 10 Eczymes Fat Chain Breaker.

pill 1 acid I II

1 360.00 g D 75 26.70 g propionic acid 2 360.00 g D 75 32.51 g acetic acid 3 360.00 g D 75 21.67 g 25.98 g ethyl hexanoic acid

15 K

4 \

Eczema equivalent EDA 60% in equivalent R + B

column 1 ratio HDA ratio ° C

______ 1 0.778: 0.222 .28.10g 67.33 g HDA 0.575: 0.425 117 2 0.7: 0.3 40.74 g 38.09 g IRD 0.75: 0.25 119 3 0.7: 0 , 2: 0.1 43.46 g 13.38 g 0.8: 0.2 88

PrDA

25 in o 4 * - 97 30 HDA = 1,6-diaminohexane

PrDA ^ 3 = 1,3-diaminopropane EDA = 1,2-diaminoethane IPD = 1-aryllno-3-airaminamethyl-3,5,5-thimethylcyclohexane R + B = Annealing according to the ring and sphere method D 75 = dimerized. fatty acid with a dimer content of 75% h = commercial product on the basis of dimeric fatty acid, amines, chain switches, the exact composition of which is not

Ir / wiMAn 10

DK 156662 B

Table 2 Example of Ethernol Fortune Crinkle Block Point

Table 1 partiality,% resin test ° C

1 <1.0 1-2 65 2 <1.0 1 60 3 <1.0 2 50 10 4 <1.0 2 50 5 <1.0 2 65 6 <1.0 1-2 75 7 <2 , 0 2 55 8 <1.0 1-2 55 15 9 <1.0 1-2 50 10 <1.0 1-2 60 11 <1.0 1-2 55 12 <1.0 2 60 13 < 1.0 1-2 55 20 14 <1.0 2 55 15 <1.4 1-2 60 16 <1.4 2 60 25

Comparative Example from Table 1 30 x 8.9 2-3 70 2 <1.0 4-5 65 3 5.6 4 - 5 60 4 <1.5 3 50 35 11

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All the polyamide resins listed in Table 1 according to the invention are then treated and tested, as described in the following section.

5

Testing the ethanol dilution 3 g of polyamide resin is placed in a 500 ml Erlenmeyer flask and dissolved with stirring in 7 grams of ethanol. Then add 10 pure ethyl alcohol from a burette until the initially clear solution shows the first signs of fuzziness.

The ethanol dilution is indicated in% polyamide resin contained in the diluted just yet clear solution (see Table 2).

Preparation of inks and inks 30 g of polyamide resin are dissolved in 70 g of ethanol with stirring in a 500 ml erlenmeyer flask. Then place the solution in a measuring cup beaker and add 10 g of an organic red pigment. After 20 minutes of dispersion time, the color is poured back into the pre-used Erlenmeyer flask and diluted with ethenol for printing viscosity (20-22 seconds elapsed time in DIN 4 beaker).

The finished inks thus obtained are then printed with a commercially available laboratory printing machine from roll on 3Q roll as well on polyethylene as well as on unpainted cellular glass foil. After 2 days of storage at room temperature, the pressures are subjected to the studies described below.

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Testing of film (a), "Crinkle" test 5

This test is done to immerse the obtained, stored polyethylene printing films for 24 hours in water of 20 - 23 ° C and then immediately after recording from the medium to rub the print image against the print image with the palms under pressure and to kr011e.

10

Assessment 1. The printing film is complete 2. The printing film exhibits scratches 3. The printing film exhibits at least 10 cut places 15 4. The printing film is practically 0 laid 5. The printing film 10 is already stained without rubbing (see Table 2).

B) Block point

Pieces of the stored on unpainted cell glass applied pressure are held against each other and placed between two plant-cut glass surfaces. These are then stored under a load of 60 g / cm2 at elevated temperatures in a drying cabinet daily at about 10 ° C.

The assessment criterion is the temperature at which the film after the unfolding showed the first very slight damage (see Table 2).

35

Claims (8)

Use of alcohol-soluble polyamide-5 at room temperature produced by condensation of A) dimerized fatty acids with B) monocarboxylic acids and io C) ethylenediamine and D) unbranched co-diamine, and fald given decrease E) inorganic and / or organic pigments and / or soluble dyes, waxes, lubricants, antioxidants, nitrocellulose, and / or blended resins, as printing ink binder for printing inks, characterized in that component A is made of dimerized fatty acids having 16-24 carbon atoms, component B comprises B 1) at least one aliphatic, unbranched monocarboxylic acid of 3-6 carbon atoms, and 2) at least one aliphatic, branched monocarboxylic acid of 4-9 carbon atoms, wherein the equivalent ratio of components A to B varies. are in the range of 0.73: 0.27 to 0.6: 0.4 and each of the components B 1) and B 2) is present in amounts of at least 0.1 equivalents calculated on the total amount of acid equivalents that the component D is hexamethylenediamine and that the equivalent ratio of components C to D ranges from 0.7: 0.3 to 0.4: 0.6. The use of alcohol-soluble polyamides at room temperature according to claim 1, characterized in that the equivalence ratio of components A: B = 0.7: 0.3. Use of alcohol-soluble polyamides at room temperature according to claims 1-2, characterized in that propionic acid and / or n-valonic acid and / or n-capric acid are used as 10 monocarboxylic acids according to B 1). Use of alcohol-soluble polyamides at room temperature according to claims 1-2, characterized in that butyric acid is used as monocarboxylic acids according to B 1). Use of alcohol-soluble polyamides at room temperature according to claims 1 - 2, characterized in that as 3-methylsuccinic acid and / or 2-ethylhexanoic acid, as monocarboxylic acid according to B 2) is used. Use of alcohol-soluble polyamides at room temperature according to claims 1-5, characterized in that inorganic and / or organic pigments, soluble dyes and blended resins are used together. Use of alcohol-soluble polyamides according to claims 1-6 as room solutions in aliphatic alcohols having 2-4 carbon atoms having a solids content of approx. 20 - 50% 30 corresponding to a lapse time of 15 - 30 seconds, for deep or flexo printing. Use of alcohol-soluble polyamides at room temperature according to claims 1-7 in ethanol having a solids content of 25 to 35%, corresponding to a lapse of 18 to 25 seconds, for deep or flexo printing.